Certain water-soluble high molal oxyalkylated esters



Patented Nov 21,

CERTAIN WATER-SOLUBLE HIGH MOLAL OXYALKYLATED ESTERS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignorl to Petrolite Corporation, Ltd., W

ilmlngton, DeL,

a corporation of Delaware No Drawing. Original application March 21,

1941, Serial No. 384,596. Divided and this application June 26, 1942, Serial No. 448,683

6 Claims. (Cl. 260-485) This invention relates to a new chemical product or compound, our present application being a division of our co-pending application Serial No. 384,596, filed March 21, 1941, which substantially matured as U. S. Patent No. 2,295,165, dated September 8, 1942.

One object of our present invention is to pro vide a new material, compound or composition of matter, that is capable of use for various purposes, and particularly adapted for use as a demulsifier in the resolution of crude oil emulsions.

Another object of our invention is to provide a practicable method for manufacturing said new material, compound or composition of matter.

The new chemical compound or composition of matter which constitutes our present invention is exemplified by acidic, or preferably, the neutral ester derived by complete esteriflcation of one mole of a, polyalkylene glycol of the kind hereinafter described, with two moles of a fractional ester derived from a hydroxylated material of the kind herein described, and a polybasic carboxy acid having not over six carbon atoms? If a hydroxylated material, indicated by the sake of convenience by the formula T.OH, is reacted with a polybasic carboxy acid, which, similarly, may conveniently 'be indicated as being of the dibasic type, by the formula HOOC.D.COOH, then the fractional ester obtained by reaction between equimolar quantities may be indicated by the following formula:

HOOC.D.COO.T

The polyethylene glycol may be characterized by materials of th kind such as heptaethylene glycol, octaethylene glycol, nonaethylene'glycol, decaethylene glycol, to and including heptadecaethylene glycol. For convenience, these polyethylene glycols may be indicated by the following formula:

OH(C2H4O) mH in Which m varies from 7 through 17.

Instead of polyethylene glycols, one may use polypropylen glycols or polybutylene glycols. Thus, for convenience, in the broadest aspect,

the polyalkylene glycols employed may be lndicated by the following formula:

H(C11H2no) mH kind above described, with two moles of a fractional ester of the kind previously described. The formation of the compound may be indicated by the following reaction, although obviously, it is immaterial what particular procedure is employed to produce the particular chemical compound or product:

As indicated previously, the polybasic acids employed are limited to the type having not more than six carbon atoms, for example, oxalic, malonic, succinic, glutaric, and adipic. Similarly, one may employ acids such as fumaric, maleic, glutaconic, and various others, including citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed is usually concerned largely with convenience of manufacture of the finished ester, and also of the price of the reactants. Generally speaking,

not.

the higher the temperature employed, the easier it is to obtain large yields of the esterified prod- Although oxalic acid is comparatively cheap, it decomposes somewhat readily at slightly above the boiling point of water. For this reason, it is more desirable -to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For this reason, maleic anhydride is particularly adaptable; and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis.

Succinic acid or the anhydrlde has many of the attractive qualities ofmaleic anhydride; and this is also true of adipic acid. For purposes of brevity, the bulk of the compounds hereinafter illustrated will refer to the use of maleic anhydrlde, although it is understood that any other suitable polybasic acid may be employed. Furthermore, for purposes of convenience, reference is made to the use of polyethylene glycols. As has been previously indicated, such glycols can. be replaced by suitable polypropylene or polybutylene compounds.

As far as the range of oxyalkylated compounds employed as reactants is concerned, it is our preference to employ those having approximately 8-12 oxyalkylene groups, particularly 8-12 oxyethylene groups. The preference to use the 'oxyethylated compounds is due largely to the fact that they are commercially available, and par. ticularly so in two desirable forms. ,The most desirable form is the so-called nonaethylene glycol, which although consisting largely of nonaethylene glycol, may contain small amounts of heptaethylene and octaethylene glycols, and possibly, minor percentages of the higher homologs. Such glycols represent the upper range of distillable glycols; and they may be conveniently referred to as "upper distillable ethylene glycols."

There is no particularly good procedure for making a. sharper separation on a commercial scale; and it is understood that mixtures of one or more of the glycols may be employed, as well as a single glycol. As pointed out, it is particularly prgferred to employ nonaethylene glycol as commercially available, although it is understood that this product contains other homologs, as indicated.

substantially as desirable asthe upper distillable polyethylene glyools, are the lower non-distillable polyethylene glycols. These materials are available in the form of a waxy water-soluble material, and the general range may vary somewhat from decato tetradecaethylene glycol. As is well understood, the method of producing such glycols would cause some higher homologs to be formed; and thus, even in this instance there may be present some oxyethylene glycols within the higher range above indicated. One need not point out that these particular compounds consist of mixtures, and that in some instances, particularly desirable esters are obtained by making mixtures of the liquid nonaethylene glycol with the soft waxy, lower non-distillable polyethylene glycols. For the sake of convenience, reference in the examples will be to nonaethylene glycol; and calculations will be based on a theoretical molecular weight of 414. Actually, in the manufacture the molecular weight of the glycol employed, whether a higher distillable polyethylene glycol, or a lower non-distillable polyethylene glycol, or a mixture of the same, should be determined and reaction conducted on the basis of such determination, particularly in conjunction with the hydroxyl or acetyl value.

It has been previously pointed out that it is immaterial how the compounds herein contemplated are manufactured, although we have found it most desirable to react the selected glycol or mixtures of glycols with maleic anhydride in a ratio of two moles of the anhydride for one mole of the glycol. Under such circumstances, we have found little tendency to form longer chain polymers; and in fact, the product'of reaction, if conducted at reasonably low temperatures, appears to be largely monomeric. For convenience, such intermediate product may then be considered as a dibasic or polybasic acid. One mole of the intermediate so obtained is then reacted with two moles of the alcoholic-material of the kind subsequently described.

It is to be noted, however, that if one prepares a fractional acidic ester, then if two moles of the fractional acidic ester are reacted with one mole of the polyethylene glycol, there is no possibility for the formation of polymeric types of esteriflcation products under ordinary conditions.

The alcoholic compounds employed as reactants in the manufacture of the present compounds,

are materials commonly referred to as high molal alcohols. They are invariably water-insoluble.

more than one hydroxyl group. Such alcohols are generally obtained by reduction of the corresponding fatty acids or esters thereof. The reaction in its briefest form may be indicated as follows:

R.COOH inthe above instance may represent any detergent-forming acid, i. e., any of a num-- ber of monocarbox acids having more than 19 and not over 32 carbon atoms, and characterized by the fact that they combine with alkalies such as caustic soda, caustic potash, ammonia, triethanolamine, and the like, to produce soap or soaplike materials. The best examples are, of-course, the higher fatty acids, such as oleic acid, stearic acid, palmitic acid, etc. In addition to the high er fatty acids, other well known members include resinic acids, abietic acids, naphthenic acids, and acids obtained by the oxidation of petroleum hydrocarbons and commonly referred to as oxidized wax acids. Generally speaking, the higher fatty acids are apt to contain from 12-14 carbon atoms as a lower limit, and from 18-22 carbon atoms as an upper limit. Oxidized waxes may contain as many as 32 carbon atoms. These various acids, when unsaturated, may be totally or partially hydrogenated and then converted into the corresponding alcohol.

The commonest use of high molal alcohols has been their conversion into sulfates or sulfonates. As to patents which specifically enumerate high molal alcohols applicable for use as reactants in the manufacture of the present compound, see the following:

U. S. Patent Nos. 2,110,848, dated Mar. 8, 1938, De Groote; 2,181,172, Oct. 4, 1932, Daimler et al.; 1,916,776, July 4, 1938, Steindorff et al.; 2,106,242, Jan. 25, 1938, De Groote et el.; 2,106,243, Jan. 25, 1938, De Groote et al.; 2,110,847, Mar. 8, 1938, De Grootey 2,000,994, May 14, 1935, Schrauth; 2,061,617, Nov. 24, 1936, Downing et al.; 2,061,618, Nov. 24, 1936, Downing et al.; 2,061,619, Nov. 24, 1936, Downing et al.; 2,061,620, Nov. 24, 1936, Downing et al.; 2,171,117, Aug. 29, 1939, Schrauth et al.; 2,187,338, Jan. 16, 1940, Werntz; 2,187,339, Jan. 16, 1940, Werntz; 1,917,255, July 11, 1933, Harris; 2,170,380, Aug. 22, 1939, Holsten; 1,966,- 187, July 10, 1934, Schirm.

Chemically, it is to be noted that these alcohols represent more than one type, i. e., they include aliphatic, alicyclic, aralkyl, etc. Particularly of interest are those derived from naphthenic acids, oxidized wax acids, and by the total or partial hydrogenation of high molal aromatic alcohols or equivalent procedure. Any of the various high molal water-insoluble alcohols occurring naturally in waxes in combined form, may be employed.

As specific examples, mention may be made of the following alcohols: Decyl, undecyl, dodecyl, tetradecyl, oct-adecyl, cetyl, oleyl, cholesterol,

' glycols of high molecular weight of the type ex- They contain at least '10 carbon atoms and not emplified by octadecane diol, octamethyl glycol, decamethyl glycol, and also alkyl, cycloalkyl, aralkyl, or aryl ethers of the difierent polyhydric alcohols, such as, for example, the cresylic, phenylic, benzylic, cyclohexylic, or naphthylic ethers or glycol or glycerol. Similarly, derivatives of diphenyl, such as hydroxy diphenyl, and the hydroaromatic homologs, are suitable.

The materials herein contemplated may be illustrated further by the following examples:

Intermediate product, Example 1 Onepound mole of nonaethylene glycol is reacted with two pound moles of maleic anhydride so as to form nonaethylene glycol dihydro- 'sen dimaleate.

Intermediate product, Example 2 A. mixture or lower non-distillable polyethylene glycols, representing approximately decato tetradeca-ethylene glycol, is substituted for nonaethylene glycol in the preceding example.

Intermediate product, Example 3 A 50-50 mixture of nonaethylene glycoland lower non-distillable polyethylene glycols of the kind described in theprevious example is substituted for none-ethylene glycol in Example 1.

Intermediate product, Example 4 Adipic acid is substituted for, maleic anhydride in Examples 1-3, preceding.

Intermediate product, Example Oxalic acid is substituted for maleic anhydride in Examples 1-3, preceding.

Intermediate product, Example 6 Citric acid is substituted for maleic anhydrid in Examples 1-3, preceding.

Intermediate product, Example 7 Buccinic anhydride is substituted for maleic anhydride in Examples 1-3, preceding.

The method of producing such fractional esters is well known. The general procedure is to employ a temperature above the boiling point of water and below the pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esteriflcation step. If

desired, an inert gas, such as dried nitrogen or dried carbon dioxide, may be passed through the mixture. Sometimes it is desirable to add an esteriflcation catalyst, such as sulfuric acid, ben. zene sulfonic acid, or the like. This is the same ter is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed tocarry oi! the water formed. The mixture of xylene vapors and water vapors can becondensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. This is a conventional and well known procedure and re-- quires no further elaboration.

Composition of matter, Example 1 One pound mole of the intermediate product of the End described in Intermediate product, Examples 1, 2 and 3, above, is reacted with two pound moles of decyl alcohol until all carboxyl acidity has disappeared. Time of reaction may vary from a few hours to as much as 20 hours.

Composition of matter, Example 2 Dodecyl alcohol is substituted for decyl alcohol in the preceding example.

Composition of matter, Example 3 Cetyl alcohol is substituted for decyl alcohol in Composition of matter, Example 1.

Composition of matter, Example 4 Tetradecyl alcohol is substituted for decyl alcohol in Composition of matter, Example 1.

Composition of matter, Example 5 Octadecyl alcohol is substituted for decyl alcohol in Composition of matter, Example 1. 1

Composition of matter, Example 6 Mixed alcohols derived from cocoanut oil fatty acidsare substituted for decyl alcohol in Composition of matter, Example 1.

Composition of matter, Example 7 Oleyl alcohol is substituted fordecyl alcohol in Composition of matter, Example 1.

Composition of matter, Example 8 Octadecanediol is substituted for decyl alcohol in Composition of matter, Example 1.

Composition of matter, Example 9 A mixture of naphthenyl alcohols derived from naturally-occurring naphthenic acids and having a carbon atom range approximating 16-25 carbon atoms, is substituted for decyl alcohol in Composition of matter, Example 1.

Composition of matter, Example 10 Alcohols derived from abietic acid are substituted for decyl alcohol in Composition of matter, Example 1. V

Composition of matter, Example 11 Alcohols derived from oxidized wax acids or having a carbon atom range of 16-20 carbon atoms are substituted for decyl alcohol in Composition of matter, Example 1.

Composition of matter, Example 12 The same procedure is followed as in Composition of matter, Examples 1-11, inclusive, ex-

.cept that an intermediate product of the kind exemplified by Intermediate product, Example 4,

is substituted for that in Intermediate product.

Examples 1, 2 and 3.

Composition of matter,ExampZe 13 The same procedure is followed as in Composition of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplified by Intermediate product, Example 5, is substituted for that in Intermediate product, Examples 1, 2 and 3.

Composition of matter, Example 14 The same procedure is followed as in Composition of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplified by Intermediate product, Example 6, is substituted for that in Intermediate product, Examples 1, 2 and 3.

Composition of matter, Example 15 The same procedure is followedas in Composition of matter, Examples 1-11, inclusive, except that an intermediate product of the kind eXemplifled by Intermediate product, Example 7, is substituted for that in Intermediate product, Examples 1, 2 and 3.

It is to be noted that this second step is an esteriflcation reaction, and the same procedure 4 a,ses,oas

is employed as suggested above in the prolific-don of the intermediate product. Needless to say, any particular method may he used to produce the desired compounds of the kind indicated In some instances it may be desirable to conduct the esteriiication reaction in the presence of a nonvolatile inert solvent which simply acts as a diluent or viscosity reducer.-

In the preceding examples, attention has been directed primarily to the monomeric form, or at least, to the form in which the biiunctional alco- 1101, i. e, a glycol, and the poly-functional acid, usually a birunctional compound, react to give a chain type compound in which the adjacent acid and-glycol nucleus occur as a structural unit.- For instance, in the monomeric form this may be indicated in the following manner:

acid glycol acid If, however, one prepared an intermediate product employing the ratio of three moles of maleic anhydride and two moles of nonaethylene glycol, the tendency would be to produce a prodduct which might be indicated in the following manner:

acid glycol acid glycol acid Similarly, three moles of the glycol and four moles of the :acid might tend to give a combination which may be indicated "thus:

acid glycol acid glycol acid glycol acid Another way of stating the matter is that the composition may be indicated in the following manner:

TOOC.D.COO1[ (C2H4Ol .mhCiHiOOQDlCOOleT in which the characters have their previous significance and :1: a relatively small whole number less than 1'0 and probably less than v5; and in the monomeric form :r, of course, is 1. The limitations on the size of a: are probably influenced largely by the fact that reaction leading to further growth is dependent upon random contact.

Some of the products are seli-emulsifiable oils, or seli-emidsiiiable compounds; whereas, others give cloudy solutions or sols; and the most dosirable type is characterized by giving :a clear solution in water, and usually in'the presence of soluble calcium or magnesium salts, and frequently in the presence of significant amounts of either acids or alkalies.

Water solubility can he enhanced in a number of ways which have been suggested by previous manufacturing directions, for instance:

in) By using a more highly polymerized ethylene glycol;

(b) By using a polymeric form instead of a monomeric form in regard to the unit which forms the chain between the two alcoholic nuclei;

(0) By using a polybasic carboxyacid of lowermolecular weight, tor instance, maleic acid, in stead of adipic acid;

(d) By using an alcoholic material of lower molecular weight, for instance, decyl alcohol, instead :of octadecyl alcohol.

In any event, it is to be noted that the compounds of the type herein contemplated are limited to the water-soluble type, i. e., those which a molecular solution.

Actually, a reaction involving an alcohol and an acid lestcriiication) may permit small amounts of either one or both of the reactants depending upon the predetermined proportion, to remain in anunreactedstate. lhthe actual preparationoi compositions of the kind herein contemplated, any residual acidity can be removed by any suitii able base, for instance, ammonia, triethanolamine,

1 is no obieciion to the pr se ce of th a id c ar unii a tribasic acid be employed in such a manner as to leave one tree carbonyl group, then it is desirable to neutralize such group by means oi a suitable basic material.

'15 In the hereto appended claims, reference to a neutral product refers to one in which free carboxylic radicals are absent.

Materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader the application of asphalt in road building and the like, as a constituent of soldering iiux preparations; as a flotation reagent in the flotation separation of various materials; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and

various trade wastes and the like; as germicides, insecticides, emulsifiers for cosmetics. Spray oils, water-repellent textile etc. These uses are by no exhaustive.

However, the most important phase of the present invention, as iar as industrial application goes, is concerned with the use of the materials p.'"eviousl y described as demulsifiers .f-or water-finoil emulsions, and more specifically, emulsions of 40 water or brine crude petroleum.

We have found that the particular chemical compounds or reagents herein described and desirable .ior use as demulsifiers, may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline. See U. is. Patent No. 2,157,223,, dated May "9, 1939,, to Sutton.

Chemical compounds of the kind herein dey scribed are also of value as surface tension de- 5 pressants in the :acidization of calcareous oil-beaning strata by means of strong mineral acid, such ashydrochloric and. Similarly, some members are effective as surface tension depressants or wetting agents in "the flooding of exhausted oilhearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil :irom subterranean strata, reierence made to the procedure described in detail in U, 55. Patent No.

2,226,119, dated December 24, 1940., to De Groote so strata, reference is made to U. Patent No.

.,'38'3, dated February :25, lf941,,-to De Groote and Keiser.

It will apparent to those skilled in the art that residual carboxyl acidity can be eliminated m by esteriiication with :a low molal alcohol, for inare self-emulsifying in water or produce a sol or stance, ethyl, methyl, or pmDyl alcohol, by conventional procedure, so as to give a substantially neutral product. The introduction of such low molal hydrophobe groups does not seriously aflect 7c the solubility, and in some instances, gives inpolybaslc carboxy acid having not more than 6 creased resistance to soluble calcium and magnesium salts, forsuch property is of particular value. Usually, however, neutralization with a dilute solution of ammonia or the like is Just as practicable and less expensive.

Having thus described our invention, what we 'claim as new and desire to secure by Letters carbon atoms; and the ratio or the esterifying reactants being within the range of more than 1.

and not over 2 moles of the polybasic acid for each'mole of the glycol,

4. A neutral water-soluble esterification product derived by reaction between one mole of a dibasic compoundand two moles of a high molal water-insoluble alcoholhaving at least carbon atoms and not more than 22 carbon atoms; the dibasic compound being the esterification product of: (.A) a polyalkylene glycol having at least 7 and not more than 1'1 ether linkages, and the compound being the esterification product of:

(A) a polyalkylene glycol having at least 7 and not more than 1'7 ether linkages, and the alkylene radical thereof containing at least 2 and not more than 6 carbon. atoms; and (B) a poly-basic carboxy acid having not more than 6 carbon atoms; and the ratio of the esterifying reactants being within the range of more than 1 and not over 2 moles of the polybasic acid for each mole of the glycol.

2. A water-soluble esterification product derived by reaction between one mole of a polybasic compound and two moles of a high molal water-insoluble alcohol having at least 10 carbon atoms and not more than 22 carbon atoms; the polybasic compound being the esteriflcation product of: (A) a polyalkylene glycol having at least '7 and not more than 1'7 ether linkages, and the alkylene radical thereof containing at least 2 and not more than 6 carbon atoms; and (B) a polybasic carboxy acid having not more than 6 carbon atoms; and the ratio of the esterifying reactants being within the range of more than 1 and not over 2 "moles of the polybasic acid for and not more than 17 ether linkages, and thealkylene radical thereof containing at least 2 and not more than 6- carbon atoms; and (B) a alkylene radical thereof containing at least 2 and not more than 6 carbon atoms; and (B) a dibasic carboxy acid having not more than 6 carbon atoms; and the ratio or the esterifying reactants being within the range of more than 1 r and not over 2 moles of the dibasic acid for each mole of the glycol.

5. A neutral water-soluble esterification product derived by reaction between one mole of a dibasio' compound and two moles of a high molal water-insoluble alcohol having at least 10 carbon atoms and not more than 22 carbon atoms; the dibasic compound being the esterification product of i (A) a polyethylene glycol having at least '1 and not more than 17 ether linkages; and (B), a dibasic carboxy acid having not more than 6 carbon atoms; and the ratio of the esterifying reactants being withinthe range of more than 1 and not over 2 moles of the dibasic acid for each mole of the glycol. A

6. A neutral water-soluble esterification product derived by reaction between one mole of a dibasic compound and two moles of a high molal water-insoluble aliphatic alcohol having at least 10 and not more than 18 carbon atoms; the dibasic compound being the esterification product or: (A) a polyethylene glycol having at least 'ly and not more than 1'7 ether linkages; and (B) a dibasic carboxy acid having not more than 6 carbon atoms; and the ratio of the esterifying reactants being within the range of more than 1 and not over 2 moles of the dibasic acidtor each mole of the glycol.

. MELVIN DE GROOTE.

.BERNHARD KEISER. 

